JP2002179901A - Polycarbonate resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polycarbonate resin composition having an excellent dust-adhesion preventive characteristic and antistatic property as well as a high degree of transparency and an improved yellowing. SOLUTION: The polycarbonate resin composition, containing 0.0001 to 10 pts.wt. of (B) a phosphonium sulfonate salt relative to 100 pts.wt. of (A) a polycarbonate resin, is characterized in that the polycarbonate resin composition is made by melt-kneading (A) the polycarbonate resin and (B) the phosphonium sulfonate salt in the presence of (C) water of more than 0.01 pt.wt. to less than 0.2 pt.wt. relative to 100 pts.wt. of the polycarbonate resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a polycarbonate resin composition and a molded product thereof. More specifically, the present invention relates to a polycarbonate resin composition suitable for use in preventing dust from adhering.

[0002]

BACKGROUND OF THE INVENTION Polycarbonate resins are used in various fields because of their excellent transparency, heat resistance and mechanical strength. For example, automotive headlamp lenses, covers and lenses for various lighting equipment, transparent films or sheets, optical disk substrates and cartridges, OA equipment, office equipment, various parts of home appliances, storage and transport case materials, etc. Headlamp lenses, covers and lenses for various lighting equipment, transparent films or sheets, optical disk bases and cartridges, OA
It is used in various fields, including applications such as various parts of equipment, office equipment, and home electric appliances, and case materials for storage and transportation.

[0003] When a molded article made of such a polycarbonate-based resin is used, there is a problem that the molded article is contaminated by external fine dust. Therefore, it has been desired to prevent such adhesion of dust without impairing the transparency. So, for example,
It is known that an antistatic agent such as a phosphonium sulfonate is added to a polycarbonate resin to improve the antistatic property of the polycarbonate resin and suppress the adhesion of dust. However, when an antistatic agent is added, there is a problem that yellowing of a polycarbonate molded product is caused and the hue of the molded product is impaired. Such yellowing is a serious problem, particularly in applications requiring transparency, because it impairs commercial value.

For the purpose of improving the yellowing, a method of adding a phosphite together with a phosphonium sulfonate (Japanese Patent Publication No. 7-39537) has been proposed.
The improvement of the yellowing of the polycarbonate resin is not always sufficient, and further improvement of the yellowing has been demanded. As a method for suppressing yellowing of a polycarbonate resin molded product, Japanese Patent Publication No. Hei 5-27647 discloses that 0.2 to 2 parts of water is added to 100 parts by weight of a polycarbonate resin powder.
It is disclosed that by adding 0 parts by weight and kneading and extruding under conditions that do not cause hydrolysis of the polycarbonate, the content of volatile impurities contained in the polycarbonate resin is reduced to suppress yellowing. . However,
In the resin molded product obtained by this method, although the yellowing is certainly suppressed, the antistatic property of the polycarbonate resin molded product itself is insufficient, and it is difficult to apply the application to the above-mentioned dust-breaking application. There was a problem.

[0005] Under such circumstances, the present inventors have desired the appearance of a composition capable of producing a polycarbonate molded article having excellent hue stability and excellent antistatic properties without yellowing. I was

[0006]

OBJECTS OF THE INVENTION The present invention provides excellent dust-prevention properties,
It is another object of the present invention to provide a polycarbonate resin composition having high anti-static properties, high transparency, and improved yellowing.

[0007]

SUMMARY OF THE INVENTION The polycarbonate resin composition according to the present invention comprises (A) 1000001 parts by weight of a polycarbonate resin, and (B) a phosphonium sulfonate salt of 0.0001-1.
0 parts by weight, the polycarbonate resin composition,
(A) a polycarbonate resin and (B) a phosphonium sulfonate salt in an amount of 0.01 to less than 0.2 parts by weight of (C) based on 100 parts by weight of the polycarbonate resin;
It is characterized by being produced by melt-kneading in the presence of water.

[0008] The polycarbonate resin composition according to the present invention comprises (A) a polycarbonate resin and (B) a phosphonium sulfonate, and
It is obtained by melting and kneading in the presence of 0.01 to less than 0.2 parts by weight of water (C) with respect to 00 parts by weight. The one obtained by melting and kneading the phosphonium sulfonate salt with the polycarbonate resin below has a high antistatic effect, does not cause dust to adhere to the molded product surface, and has excellent color tone and mechanical properties Molded products can be manufactured.

The amount of the water (C) is preferably in the range of 0.05 to 0.18 parts by weight based on 100 parts by weight of the polycarbonate resin. The amount of the phosphonium sulfonate (B) is preferably in the range of 0.001 to 5 parts by weight based on 100 parts by weight of the polycarbonate resin. Such a polyolefin resin composition according to the present invention is suitable for use in automotive headlamp lenses, lighting fixture covers, lighting fixture lenses, transparent sheets, and transparent films.

[0010]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the polycarbonate resin composition according to the present invention will be specifically described. The polycarbonate resin composition according to the present invention comprises (A) a polycarbonate and (B) a phosphonium sulfonate.

Polycarbonate resin (A) Polycarbonate resin (A) used in the present invention
Is an aromatic homopolycarbonate or an aromatic copolycarbonate obtained by reacting an aromatic dihydroxy compound with a carbonate precursor. The carbonate-based resin generally has a repeating structural unit represented by the following formula (1).

[0012]

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(In the above formula, A is a divalent residue derived from an aromatic dihydroxy compound.) The aromatic dihydroxy compound contains two hydroxy groups as functional groups, and each hydroxy group has an aromatic group. Mononuclear or polynuclear aromatic compounds directly bonded to a nuclear carbon atom are included. A specific example of the aromatic dihydroxy compound is a bisphenol compound represented by the following formula (2).

[0014]

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As the aromatic dihydroxy compound represented by the formula (2), specifically, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2 -Bis (4-hydroxyphenyl) propane (so-called bisphenol A), 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane , 2,2-bis (4-hydroxy-1-methylphenyl)
Propane, 1,1-bis (4-hydroxy-t-butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2- (4-hydroxy-3,5-dibromo Bis (hydroxyaryl) alkanes such as phenyl) propane; bis (hydroxyaryl) cycloalkanes such as 1,1-bis (4-hydroxyphenyl) cyclopentane and 1,1- (4-hydroxyphenyl) cyclohexane;
Dihydroxyaryl ethers such as 4,4'-dihydroxydiphenyl ether and 4,4'-dihydroxy-3,3'-dimethylphenyl ether; 4,4'-dihydroxydiphenyl sulfide and 4,4'-dihydroxy-3,3 ' -Dihydroxydiaryl sulfides such as -dimethylphenyl sulfide; 4,4'-dihydroxydiphenyl sulfide, 4,4'-
Dihydroxydiarylsulfoxides such as dihydroxy-3,3'-dimethyldiphenylsulfoxide;4,4'-dihydroxydiphenylsulfone,4,4'-dihydroxy-3,
Examples include, but are not limited to, dihydroxydiaryl sulfones such as 3′-dimethyldiphenyl sulfone.

Of these aromatic dihydroxy compounds,
In particular, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) is preferably used. Further, as the aromatic dihydroxy compound other than the above formula (2), an aromatic dihydroxy compound represented by the following formula (3) can also be used.

[0017]

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(Wherein R ^f is independently a hydrocarbon group having 1 to 10 carbon atoms, a halogenated hydrocarbon group in which at least one of the hydrocarbon groups is substituted with a halogen atom, or a halogen atom. And p is an integer from 0 to 4.) Such compounds include, for example, resorcin; and 3-methylresorcin, 3-ethylresorcin, 3-propylresorcin, 3-butylresorcin, 3-tert-butylresorcin, 3-phenylresorcinol, 3-cumylresorcinol,
Substituted resorcinols such as 2,3,4,6-tetrafluororesorcin and 2,3,4,6-tetrabromoresorcin; catechol; hydroquinone, and 3-methylhydroquinone, 3-ethylhydroquinone, 3-propylhydroquinone, 3- Butylhydroquinone, 3-t-butylhydroquinone, 3-phenylhydroquinone, 3-cumylhydroquinone, 2,3,5,6-tetramethylhydroquinone, 2,3,5,6-tetra-t-butylhydroquinone, 2, Substituted hydroquinones such as 3,5,6-tetrafluorohydroquinone and 2,3,5,6-tetrabromohydroquinone are exemplified.

Further, as the aromatic dihydroxy compound other than the above formula (2), the following formula:

[0020]

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2,2,2 ', 2'-tetrahydro-3,3,
3 ′, 3′-Tetramethyl-1,1′-spirobi- [1H-indene] -7,7′-diol can also be used. These aromatic dihydroxy compounds may be used alone or in combination of two or more. Further, the polycarbonate may be linear or branched. Further, a blend of a linear polycarbonate and a branched polycarbonate may be used.

Such a branched polycarbonate is obtained by reacting a polyfunctional aromatic compound with an aromatic dihydroxy compound and a carbonate precursor. Representative examples of such polyfunctional aromatic compounds are described in U.S. Patent Nos. 3,028,385, 3,334,154, 4,001,124 and 4,131,576, specifically,
1,1-tris (4-hydroxyphenyl) ethane, 2,2 ', 2 "-
Tris (4-hydroxyphenyl) diisopropylbenzene, α-methyl-α, α ', α'-tris (4-hydroxyphenyl) -1,4-diethylbenzene, α, α', α "-tris (4-hydroxyphenyl ) -1,3,5-triisopropylbenzene, phloroglysin, 4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) -heptane-2, 1,3,5-tri (4-hydroxy Phenyl) benzene, 2,2-bis- [4,4- (4,4'-dihydroxyphenyl) -cyclohexyl] -propane, trimellitic acid,
Examples thereof include 1,3,5-benzenetricarboxylic acid and pyromellitic acid. Of these, 1,1,1-tris (4-hydroxyphenyl) ethane and α, α ′, α ″ -tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene are preferably used.

The intrinsic viscosity of the polycarbonate resin measured at 25 ° C. in methylene chloride is not particularly limited and may be appropriately selected in consideration of the intended use and moldability. / g or more, preferably 0.30 dl / g to 0.98 dl / g, more preferably 0.1 dl / g to 0.98 dl / g.
It is in the range of 34 dl / g to 0.64 dl / g, and is usually 10,000 or more, preferably 1
2000 to 50,000, more preferably 14,000 to
It is desirable to be in the range of 30,000. In addition, a plurality of different inherent viscosity polycarbonate resins can be mixed and used.

The polycarbonate resin used in the present invention is produced by a known production method. For example, a method of synthesizing a polycarbonate by subjecting an aromatic dihydroxy compound and a carbonate precursor (eg, carbonic acid diester) to transesterification in a molten state (melting method), a method in which an aromatic dihydroxy compound and a carbonate precursor (eg, phosgene ) (Interface method).

These production methods are described, for example, in JP-A-2-175723, JP-A-2-124934, US Pat. Nos. 4,001,184, 4,238,569,
Nos. 238,597 and 4,474,999. Examples of the carbonic acid diester used in the method (melting method) (melting method) include diphenyl carbonate, bis (chlorophenyl) carbonate, bis (2,4-dichlorophenyl) carbonate, and bis (2,4,6-trichlorophenyl). ) Carbonate, bis (2-cyanophenyl) carbonate, bis (o-nitrophenyl) carbonate, ditolyl carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, diethyl carbonate, dimethyl carbonate, dibutyl carbonate, Dicyclohexyl carbonate and the like. Of these, diphenyl carbonate is preferably used. Two or more of these can be used in combination. Among these, diphenyl carbonate is particularly preferably used. Further, such a carbonic acid diester may contain a dicarboxylic acid or a dicarboxylic acid ester. Specifically, the carbonic diester is
The dicarboxylic acid or dicarboxylic acid ester may be contained in an amount of preferably 50 mol% or less, more preferably 30 mol% or less.

Such dicarboxylic acids or dicarboxylic esters include terephthalic acid, isophthalic acid,
Examples thereof include sebacic acid, decandioic acid, dodecandioic acid, diphenyl sebacate, diphenyl terephthalate, diphenyl isophthalate, diphenyl decandioate, and diphenyl dodecandioate. The carbonic acid diester may contain two or more of these dicarboxylic acids or dicarboxylic acid esters.

Polycarbonate is obtained by polycondensing the above-mentioned diester carbonate and the aromatic dihydroxy compound. In producing polycarbonate, the carbonic acid diester as described above is used in an amount of 0.95 to 1.30 mol, based on 1 mol of the aromatic dihydroxy compound in total.
Preferably, it is used in an amount of 1.01 to 1.20 mol.

In such a melting method, for example, a compound proposed by the present applicant in JP-A-4-175368 is used as a catalyst. Specifically, as a melt polycondensation catalyst,
Usually, (a) an alkali metal compound and / or an alkaline earth metal compound (hereinafter also referred to as (a) an alkali (earth) metal compound) are used.

(A) Alkali (earth) metal compounds include organic acid salts of alkali metals and alkaline earth metals;
Inorganic acid salts, oxides, hydroxides, hydrides or alcoholates are preferably used. Specifically, as the alkali metal compound, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, lithium hydrogen carbonate, sodium carbonate, potassium carbonate, lithium carbonate, sodium acetate, potassium acetate, Lithium acetate, sodium stearate, potassium stearate, lithium stearate, sodium borohydride, lithium borohydride, sodium borohydride, sodium benzoate, potassium benzoate, lithium benzoate, disodium hydrogen phosphate, phosphoric acid Dipotassium hydrogen, dilithium hydrogen phosphate, bisphenol A
Disodium salt, dipotassium salt, dilithium salt, phenol sodium salt, potassium salt, lithium salt and the like. Examples of the alkaline earth metal compound include calcium hydroxide, barium hydroxide, magnesium hydroxide, water Strontium oxide, calcium bicarbonate, barium bicarbonate, magnesium bicarbonate, strontium bicarbonate, calcium carbonate, barium carbonate, magnesium carbonate, strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, Examples include magnesium stearate and strontium stearate. Two or more of these compounds can be used in combination.

Such an alkali (earth) metal compound is used in an amount of 1 × 10 ⁻⁸ to 1 × 1 mol per bisphenol.
X 10 ^-3 mol, preferably 1 x 10 ^-7 to 2 x 10 ^-6 mol, more preferably 1 x 10 ^-7 to 8 x 10 ^-7 mol, contained in the melt polycondensation reaction. It is desirable.
Further, when an alkali (earth) metal compound is previously contained in the bisphenol as a raw material of the melt polycondensation reaction, the amount of the alkali (earth) metal compound present at the time of the melt polycondensation reaction is reduced to 1 It is desirable to control the addition amount so as to be within the above range with respect to the mole.

As a melt polycondensation catalyst, a basic compound (b) may be used in addition to the above-mentioned (a) alkali (earth) metal compound. Examples of such a basic compound (b) include a nitrogen-containing basic compound which is easily decomposed or volatile at a high temperature, and specific examples thereof include the following compounds.

Tetramethylammonium hydroxide (Me ₄ NOH), tetraethylammonium hydroxide (Et ₄ NOH), tetrabutylammonium hydroxide (Bu ₄ NOH), trimethylbenzylammonium hydroxide (φ-CH ₂ (Me) ₃ NOH ), Such as alkyl, aryl,
Ammonium hydroxides having an araryl group and the like, tertiary amines such as trimethylamine, triethylamine, dimethylbenzylamine and triphenylamine, R ₂ NH (where R is an alkyl group such as methyl and ethyl, and aryl such as phenyl and tolyl) A primary amine represented by RNH ₂ (where R is as defined above), 4-dimethylaminopyridine, 4-diethylaminopyridine, 4-pyrrolidinopyridine, etc. Pyridines, imidazoles such as 2-methylimidazole and 2-phenylimidazole, or ammonia, tetramethylammonium borohydride (Me ₄ NBH ₄ ), tetrabutylammonium borohydride (Bu ₄ NBH ₄ ), tetrabutylammonium tetraphenyl Borate (Bu ₄ NBPh ₄ ), Basic salts such as tetramethylammonium tetraphenylborate (Me ₄ NBPh ₄ ).

Of these, tetraalkylammonium hydroxides are preferably used. As above
(b) The nitrogen-containing basic compound is used in an amount of 1 × 10 ^-6 to 1 × 10 ^-1 mol, preferably 1 × 1 ^-1 mol, per mol of bisphenols.
It can be used in an amount of 0 ^-5 to 1 × 10 ^-2 mol.

Further, a boric acid compound (c) can be used as a catalyst. Examples of such a (c) boric acid compound include boric acid and boric acid esters. Examples of the borate ester include a borate ester represented by the following general formula.

B (OR) _n (OH) _{3-n In the} formula, R is alkyl such as methyl and ethyl, aryl such as phenyl, and n is 1, 2 or 3.
Specific examples of such borate esters include trimethyl borate, triethyl borate, tributyl borate,
Examples include trihexyl borate, triheptyl borate, triphenyl borate, tolyl borate, and trinaphthyl borate.

Such boric acid or boric acid ester (c) is used in an amount of 1 × 10 ⁻⁸ to 1 mol per bisphenol.
It can be used in an amount of 1 × 10 ^-1 mol, preferably 1 × 10 ^-7 to 1 × 10 ^-2 mol, more preferably 1 × 10 ^-6 to 1 × 10 ^-4 mol. Examples of the melt polycondensation catalyst include a combination of (a) an alkali (earth) metal compound and (b) a nitrogen-containing basic compound, and further comprising (a) an alkali (earth) metal compound and (b) a nitrogen-containing compound. It is preferable to use a combination of the basic compound and (c) boric acid or a borate ester.

When the above amount of (a) an alkali (earth) metal compound and (b) a nitrogen-containing basic compound are used in combination as a catalyst, the polycondensation reaction can proceed at a sufficient rate. It is preferable because it can produce a high molecular weight polycarbonate with high polymerization activity. When (a) an alkali (earth) metal compound and (b) a nitrogen-containing basic compound are used in combination, or (a) an alkali (earth) metal compound and (b) a nitrogen-containing basic compound and (c) ) When boric acid or boric acid ester is used in combination, a mixture of each catalyst component may be added to a molten mixture of bisphenols and carbonic acid diester. It may be added to the mixture.

Examples of the carbonate precursor used in the interface method of [Interface Method] include carbonyl halide, diaryl carbonate, and bishaloformate, and any of them may be used. Examples of the carbonyl halide include carbonyl bromide, carbonyl chloride (so-called phosgene), and a mixture thereof. Examples of the aryl carbonate include diphenyl carbonate, diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, and the like. As the bishaloformate, for example, 2,
Bischloroformate or bisbromoformate of aromatic dihydroxy compounds such as 2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, hydroquinone; ethylene glycol Glycols such as bischloroformate or bisbromoformate. While any of the above carbonate precursors are useful, carbonyl chloride (ie, phosgene) is preferred.

In this interfacial method, first, the aromatic dihydroxy compound is dissolved or dispersed in an aqueous caustic solution, the resulting mixture is added with a solvent incompatible with water, and these reactants are converted to a suitable catalyst. In the presence of a particular p
This is done by contacting with a carbonate precursor such as phosgene under H conditions. Usually, methylene chloride, 1,2-dichloroethane, chlorobenzene, toluene or the like is used as a solvent that is incompatible with water used. The catalyst used in the interface method is not particularly limited, but is usually a tertiary amine such as triethylamine,
Quaternary phosphonium compounds, quaternary ammonium compounds and the like are used. The reaction temperature in the interface method is not particularly limited as long as the reaction proceeds, but is preferably in the range of room temperature (25 ° C.) to 50 ° C.

The polycarbonates obtained by these or the production methods may be end-capped with specific functional groups as required. Examples of the terminal blocking agent include, but are not particularly limited to, phenol, monovalent phenols such as chroman-I and p-cumylphenol. (B) Phosphonium sulfonic acid salt The (B) phosphonium sulfonic acid salt used in the present invention is, for example, the following formula (4):

[0041]

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[0042] (In the above formulas, R ¹ is an alkyl group or an aryl group having 6 to 40 carbon atoms of 1 to 40 carbon atoms, R ^2,
R ³ , R ⁴ and R ⁵ are each independently selected from a hydrogen atom, an alkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 10 carbon atoms). Here, the alkyl group is
Includes linear, branched or cyclic alkyl groups. The aryl group includes an alkylaryl group and an arylalkyl group. In addition, the alkyl group and the aryl group may be substituted with an arbitrary substituent.

In R ¹ , examples of the alkyl group include a dodecyl group, a decyl group, a butyl group and an ethyl group. Examples of the aryl group include a dodecylphenyl group, a phenyl group, a benzyl group, a benzyl group, a phenethyl group, a tolyl group, and a xylyl group. Among them, R ¹ is preferably an aryl group. In R ^{2 to} R ⁵ , examples of the alkyl group include groups such as methyl, ethyl, propyl, and butyl. Examples of the aryl group include a phenyl group, a benzyl group, a phenethyl group, a tolyl group, and a xylyl group.

Examples of the phosphonium sulfonate represented by the formula (4) include a tetraalkylphosphonium salt of dodecylsulfonic acid and a tetraalkylphosphonium salt of dodecylbenzenesulfonic acid. The phosphonium sulfonate (B) is used in an amount of 0.0001 to 10 parts by weight, preferably 0.001 to 5 parts by weight, more preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the polycarbonate (A). Desirably.

If the amount of (B) the phosphonium sulfonate is less than 0.0001 parts by weight, the effect of the present invention (ie, the antistatic effect) cannot be exerted, so that dust may adhere to the surface of the molded product. . When the amount of the phosphonium sulfonate (B) is more than 10 parts by weight, the heat resistance is deteriorated, the color may be changed to yellow, and the mechanical properties of the molded product may be deteriorated.

Preparation of Polycarbonate Resin Composition The polycarbonate resin composition of the present invention comprises the above (A) polycarbonate resin and (B) phosphonium sulfonate in an amount of 100 parts by weight of the polycarbonate resin.
0.01 parts by weight or more, less than 0.2 parts by weight, preferably,
It is produced by melt-kneading in the presence of 0.05 to 0.18 parts by weight of (C) water.

As the amount of water added increases, productivity may be greatly reduced due to occurrence of backflow from the inside of the extruder in the hopper of the extruder. Also,
(B) Since it contains a phosphonium sulfonate,
If a large amount of water is added, hydrolysis of the polycarbonate resin tends to occur, and the mechanical strength of the molded product may be impaired. Therefore, a preferable addition amount of water is 0.01 part by weight or more and less than 0.2 part by weight, more preferably 0.05 part by weight.
０．１0.18 parts by weight.

Further, by adding such a specific amount of water, it is possible to obtain a polycarbonate resin molded product to which dust and the like are hardly adhered, without lowering the productivity at the time of extrusion, and to obtain hue stability and transparency. And a polycarbonate resin molded article having improved yellowing can be obtained. Water may be added in advance before kneading the (A) polycarbonate resin and (B) the phosphonium sulfonate, or (A) the polycarbonate resin and (B)
It may be added during kneading with the phosphonium sulfonate. The melt-kneading of (A) the polycarbonate resin and (B) the phosphonium sulfonate in the presence of water is preferably performed while removing the volatile components and steam generated using an extruder equipped with a vent.

The apparatus for performing the melt-kneading is not particularly limited, and examples thereof include an extruder, a Banbury mixer, a roller, a kneader, and the like, and these may be operated batchwise or continuously. Such an apparatus is desirably provided with a degassing mechanism.

Other Additives The polycarbonate resin composition according to the present invention comprises (C)
Stabilizers (such as antioxidants) may be included. Phosphorous acid and / or phosphites may be included as stabilizers. The phosphite is, for example, P (OR) ₃ [where R may be the same or different, and includes an alkyl group (eg, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, etc.), a cycloalkyl group] (Eg, cyclopentyl group, cyclohexyl group, etc.), aryl group (phenyl group, etc.), aralkyl group (methylphenyl group, t-butylphenyl group, etc.) or alkaryl group (benzyl group, etc.), and these groups are May be included]. Specifically, for example, trioctadecyl phosphite, trioctyl phosphite, triphenyl phosphite, tri (2-methylphenyl) phosphite, tri (4-t-butylphenyl) phosphite, tri (2-t-butyl) Phenyl) phosphite, tri (2,6-dimethylphenyl) phosphite, tri (2,6-diethylphenyl) phosphite, tri (2-methoxy-4-t-butylphenyl) phosphite, tri (2-methyl -4-t-butylphenyl) phosphite, tri (2-nonylphenyl) phosphite, tri (2-nonyl-6-methylphenyl) phosphite, tri (2-dodecylphenyl) phosphite,
Octyl diphenyl phosphite, tri (2-dodecyl-4
-t-butylphenyl) phosphite, didecylphenylphosphite, dioctylphenylphosphite, butyldiphenylphosphite, diisopropylphenylphosphite, octyl-di (4-t-butylphenyl) phosphite, 2-methylphenyl-di (2-cyclohexylphenyl) phosphite, di (4-t-butylphenyl) -2-
Nonylphenyl phosphite, trilauryl phosphite, trilauryl thiophosphite and the like can be mentioned. Of these, triaryl phosphites and alkyl diaryl phosphites are particularly preferred. The phosphites can be used in combination of two or more.

The phosphorous acid is a polycarbonate (A) 10
It is desirable to use it in an amount of 0.0001 to 0.1 part by weight, preferably 0.0001 to 0.01 part by weight, based on 0 part by weight. If the amount of phosphorous acid used is large, it may affect moisture resistance and the like. When phosphorous acid is used as described above, a polycarbonate resin composition which is not easily discolored, and which is excellent in transparency, anti-dust property and mechanical strength can be obtained. Further, the phosphite is used in an amount of 0.0001 to 100 parts by weight of the polycarbonate (A).
It is desirable to use 0.5 parts by weight, preferably 0.001 to 0.1 parts by weight.

A hindered phenolic antioxidant may be contained as a stabilizer. Specifically, n-octadecyl-3- (3 ', 5'-di-t-butyl-4-hydroxyphenyl) propionate, 2,6-di-t-butyl-4-hydroxymethylphenol, 2,2 '-Methylenebis (4-methyl-6-t-butylphenol), pentaerythrityl-tetrakis [3- (3', 5'-
Di-t-butyl-4-hydroxyphenyl) propionate]. These may be used alone or in combination of two or more.

The hindered phenol-based stabilizer is used in an amount of 0.1 to 100 parts by weight of the polycarbonate-based resin.
It is desirable that the amount be from 0001 to 1 part by weight, preferably from 0.001 to 0.5 part by weight. An epoxy-based stabilizer may be included as a stabilizer. For example, epoxidized soybean oil, epoxidized linseed oil, phenyl glycidyl ether, allyl glycidyl ether, t-butylphenyl glycidyl ether, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexylcarboxylate, 3,4- Epoxy-6-methylcyclohexylmethyl -3 ',
4'-epoxy-6'-methylcyclohexylcarboxylate, 2,3-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexylcarboxylate, 4- (3,4-epoxy-
5-methylcyclohexyl) butyl-3 ', 4'-epoxycyclohexylcarboxylate, 3,4-epoxycyclohexylethylene oxide, cyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, 3,4-epoxy
-6-methylcyclohexylmethyl-6'-methylsilohexylcarboxylate, bisphenol A diglycidyl ether, tetrabromobisphenol A glycidyl ether, diglycidyl ester of phthalic acid, diglycidyl ester of hexahydrophthalic acid, bis-epoxydicyclo Pentadienyl ether, bis-epoxyethylene glycol, bis-epoxycyclohexyl adipate, butadiene diepoxide, tetraphenylethylene epoxide, octyl epoxy tartrate, epoxidized polybutadiene, 3,4-dimethyl-1,2-epoxycyclohexane, 3, 5-dimethyl-1,2-epoxycyclohexane, 3-
Methyl-5-t-butyl-1,2-epoxycyclohexane, octadecyl-2,2-dimethyl-3,4-epoxycyclohexylcarboxylate, N-butyl-2,2-dimethyl-3,4-epoxycyclohexylcarboxylate , Cyclohexyl-2
-Methyl-3,4-epoxycyclohexylcarboxylate, N-butyl-2-isopropyl-3,4-epoxy-5-methylcyclohexylcarboxylate, octadecyl-3,4
-Epoxycyclohexylcarboxylate, 2-ethylhexyl-3 ', 4'-epoxycyclohexylcarboxylate, 4,6-dimethyl-2,3-epoxycyclohexyl-3',
4'-epoxycyclohexylcarboxylate, 4,5-epoxytetrahydrophthalic anhydride, 3-t-butyl-4,5-epoxytetrahydrophthalic anhydride, diethyl-4,5-epoxy-cis-1,2-cyclohexyldi Carboxylate,
Di-n-butyl-3-t-butyl-4,5-epoxy-cis-1,2-cyclohexyldicarboxylate;

Such an epoxy-based stabilizer is used in an amount of from 0.0001 to 100 parts by weight of the polycarbonate-based resin.
5 parts by weight, preferably 0.001 to 1 part by weight, more preferably 0.005 to 0.5 part by weight. Further, a thiol-based or metal salt-based stabilizer can be used. Furthermore, in the polyolefin resin composition according to the present invention, the above components (A) to
In addition to (C), (D) an ultraviolet absorber may be contained.

As the ultraviolet absorber (D), a conventional ultraviolet absorber for a polycarbonate resin composition can be used.
For example, a benzotriazole-based ultraviolet absorber, a benzophenone-based ultraviolet absorber, a salicylate-based ultraviolet absorber, and the like can be given. Benzotriazole UV absorbers
For example, it is commercially available as UV5411 from Adeka Argus. The benzophenone-based ultraviolet absorber is commercially available as, for example, UV531 from Synamit. Examples of the salicylate-based ultraviolet absorber include phenyl salicylate, pt-butylphenyl salicylate, p-octylphenyl salicylate and the like.

The component (D) is used in an amount of 0.01 part by weight or more, preferably 0.05 part by weight or more and 10 parts by weight or less, preferably 5 parts by weight or less based on 100 parts by weight of the component (A). . If the amount of the component (D) is too small, the light resistance is deteriorated, and if it is too large, the heat resistance of the resin composition is reduced. In addition, for the purpose of improving the releasability of the polycarbonate resin composition, a release agent can be added. Preferred release agents are silicone-based release agents such as methylphenyl silicone oil, pentaerythritol tetrastearate, and glycerin monostearate. Ester release agents such as acrylate, montanic acid wax and polyalphaolefin, and olefin release agents.

Any of the polycarbonate resin compositions of the present invention may be mixed with other additives according to the purpose at the time of mixing and molding, as long as the physical properties are not impaired.
For example, coloring agents (pigments such as carbon black and titanium oxide, dyes such as bluing agents), reinforcing agents (glass fibers, carbon fibers, etc.), fillers (silica, millt glass,
Glass flakes, talc, clay, mica, etc.), heat-resistant agents, antioxidant inhibitors, weathering agents, lubricants, release agents, plasticizers,
Flame retardants, flow improvers and the like can be added.

The molded article obtained by molding the polycarbonate resin composition according to the present invention as described above has transparency,
Excellent mechanical strength and antistatic properties. For this reason, the polycarbonate resin composition according to the present invention is used for transparent and antistatic applications such as automotive headlamp lenses, lighting fixture covers, lighting fixture lenses, transparent sheets, and transparent films. It is suitable.

[0059]

By using the polycarbonate resin composition of the present invention, excellent hue and transparency,
A molded article having excellent mechanical strength and antistatic properties can be obtained. Such a polycarbonate resin composition of the present invention can be used as a cover or lens for a headlamp lens of an automobile or various lighting fixtures, a transparent film or a transparent sheet, a base of an optical disk or its cartridge, OA equipment, office equipment, home electric equipment, etc. It is particularly useful in applications such as parts, storage and transport case materials.

[0060]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto.
The following compounds were used in Examples and Comparative Examples. (A) Polycarbonate resin PC: Polycarbonate, manufactured by Nippon GE Plastics Co., Ltd .; trademark; lexane (intrinsic viscosity 0.50 dl / g measured in methylene chloride at 25 ° C.) (B) Sulfonate phosphonium salt Dodecylbenzenesulfonate tetrabutylphosphonium Salt, manufactured by Takemoto Yushi Co., Ltd., trademark EPA202.

Various tests and evaluations performed in Examples and Comparative Examples were performed as follows. (1) Half value (Antistatic property) An injection molded plate having a thickness of 3 mm (5 cm x 5 cm square plate) was molded at a cylinder temperature of 280 ° C and a mold temperature of 80 ° C.
Using onestmeter (S-5109, manufactured by Shishido Shokai Co., Ltd.)
The time until the charge of the charged body was reduced by half was measured as a half value (time unit: second). The smaller the half value, the better the antistatic effect.

(2) YI (Yellow Index) An injection molded plate having a thickness of 3 mm was molded at a cylinder temperature of 280 ° C. and a mold temperature of 80 ° C., and a spectrophotometer (Minolta CM-3700) was used.
Yellowness (YI) was measured using d). (3) Total light transmittance According to ASTM D1003, a 3 mm thick injection molded plate was molded at a cylinder temperature of 280 ° C and a mold temperature of 80 ° C, and the total light transmittance was measured using a spectrophotometer (Minolta CM-3700d). T%).

(4) Izod Impact Strength Izod impact strength with 1/8 inch notch was measured according to ASTM D256.

[0064]

Example 1 and Comparative Example 1 With the composition shown in Table 1, 280 ° C, 270 ° C
The mixture was melt-kneaded with a twin-screw extruder equipped with a vent set at rpm and extruded to produce pellets. Next, injection molding was performed using the obtained pellets under the conditions of a set temperature of 280 ° C. and a mold temperature of 80 ° C. The various tests described above were performed on the obtained molded product.

Table 1 shows the results.

[0066]

[Table 1]

Claims (2)

[Claims] (1) 100 parts by weight of (A) a polycarbonate resin, and (B) a phosphonium sulfonate salt of 0.000.
In the polycarbonate resin composition containing 1 to 10 parts by weight, the polycarbonate resin composition contains (A) the polycarbonate resin and (B) the phosphonium sulfonate in an amount of 0.1 to 100 parts by weight of the polycarbonate resin.
(C) A polycarbonate resin composition produced by melt-kneading in the presence of water in an amount of at least 01 part by weight and less than 0.2 part by weight. 2. The method according to claim 1, wherein (C) the amount of water is
The polycarbonate resin composition according to claim 1, wherein the amount is in the range of 0.05 to 0.18 parts by weight based on 00 parts by weight.